Predicting bond dissociation energies of cyclic hypervalent halogen reagents using DFT calculations and graph attention network model DOI Creative Commons

Yingbo Shao,

Zhiyuan Ren,

Zhihui Han

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 1444 - 1452

Published: June 28, 2024

Although hypervalent iodine(III) reagents have become staples in organic chemistry, the exploration of their isoelectronic counterparts, namely bromine(III) and chlorine(III) reagents, has been relatively limited, partly due to challenges synthesizing stabilizing these compounds. In this study, we conduct a thorough examination both homolytic heterolytic bond dissociation energies (BDEs) critical for assessing chemical stability functional group transfer capability cyclic halogen compounds using density theory (DFT) analysis. A moderate linear correlation was observed between BDEs across different centers, while strong noted among centers. Furthermore, developed predictive model machine learning algorithms. The results study could aid estimating capabilities thereby facilitating development.

Language: Английский

Diaryl hypervalent bromines and chlorines: synthesis, structures and reactivities DOI Creative Commons
Matteo Lanzi, Joanna Wencel‐Delord

Chemical Science, Journal Year: 2024, Volume and Issue: 15(5), P. 1557 - 1569

Published: Jan. 1, 2024

Diaryl hypervalent bromines and chlorines emerge as a novel foundation for advancing organic chemistry. This article provides an overview of the synthetic methodology, structural variations, latest transformations unearthed in this context.

Language: Английский

Citations

13
Organohypervalent heterocycles DOI
Ravi Kumar, Toshifumi Dohi, Viktor V. Zhdankin

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(9), P. 4786 - 4827

Published: Jan. 1, 2024

This review summarizes structural and synthetic aspects of heterocyclic molecules incorporating an atom a hypervalent main-group element. The higher thermal stability heterocycles, as compared to their acyclic analogs, adds special feature chemistry.

Language: Английский

Citations

8
Accessing unnatural α-amino acids with tetrasubstituted stereogenic centersviacatalytic enantioselective reactions of ketimine-type α-iminoesters/α-iminoamides DOI
Naoki Yasukawa, Shuichi Nakamura

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(54), P. 8343 - 8374

Published: Jan. 1, 2023

Catalytic enantioselective synthesis methodologies have been actively explored and developed owing to the significance of chiral molecules their utilities. In particular, unnatural α-amino acids with tetrasubstituted stereogenic carbon centers (α-tertiary amino acids; ATAAs) are undoubtedly among most valuable compounds. Asymmetric addition an α-iminoester or α-iminoamide is widely recognized as a straightforward, powerful, atom-economical strategy for accessing optically active derivatives. However, this type chemistry, which relies on ketimine-type electrophiles, was quite limited only few decades ago low reactivities difficulties associated enantiofacial control. This feature article comprehensively overviews research field highlights significant progress that has made. it focuses catalyst system transition state key parameters such reactions.

Language: Английский

Citations

14
Electrochemical synthesis of cyclic biaryl λ3-bromanes from 2,2’-dibromobiphenyls DOI Creative Commons
Andrejs Savkins, Igors Sokolovs

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 451 - 457

Published: Feb. 27, 2025

The remarkable nucleofugality of bromoarenes in diarylbromonium species renders them particularly suitable for the generation arynes subsequent use a wide range synthetic applications. common approach to generate cyclic biaryl λ3-bromanes is based on thermal decomposition hazardous diazonium salts. Herein, we disclose mild and straightforward by direct anodic oxidation 2,2'-dibromo-1,1'-biphenyl. electrochemical method provides access symmetrically non-symmetrically substituted moderate yields.

Language: Английский

Citations

0
Asymmetric synthesis of β-amino cyanoesters with contiguous tetrasubstituted carbon centers by halogen-bonding catalysis with chiral halonium salt DOI Creative Commons
Yasushi Yoshida,

Masahiro Aono,

Takashi Mino

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 547 - 555

Published: March 12, 2025

β-Amino cyanoesters are important scaffolds because they can be transformed into useful chiral amines, amino acids, and alcohols. Halogen bonding, which formed between halogen atoms electron-rich chemical species, is attractive of its unique interaction in organic synthesis. Chiral halonium salts have been found to strong halogen-bonding-donor abilities work as powerful asymmetric catalysts. Recently, we developed binaphthyl-based applied them several enantioselective reactions, the corresponding products high excellent enantioselectivities. In this paper, synthesis β-amino with contiguous tetrasubstituted carbon stereogenic centers by Mannich reaction through salt catalysis presented, provided yields up 86% ee. To best our knowledge, present paper first report construction catalytic reaction.

Language: Английский

Citations

0
Preparation and X-ray Structural Study of Dibenzobromolium and Dibenzochlorolium Derivatives DOI Creative Commons

Christopher D. Huss,

Akira Yoshimura, Gregory T. Rohde

et al.

ACS Omega, Journal Year: 2024, Volume and Issue: 9(2), P. 2664 - 2673

Published: Jan. 3, 2024

Various five-membered cyclic dibenzobromolium salts (dibenzo[

Language: Английский

Citations

2
Intramolecular Azo Coupling Reaction of Binaphthyl Compounds: Synthesis of Pyrazole-Containing Helicene-Like Molecules DOI
Yasushi Yoshida,

Naoyuki Aso,

Takashi Karatsu

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(19), P. 3412 - 3416

Published: May 8, 2023

A method for accessing pyrazole-containing helicene-like molecules from easily accessible NOBIN derivatives was developed. The reaction proceeded efficiently via diazonium salt intermediates, which provided a series of molecular products in yields 77%-89% regardless their steric and electronic natures. photophysical properties the were investigated. 3,3'-disubstituted showed characteristic blue shift emission spectra. Product derivatizations conducted, interesting reactivities toward nucleophiles observed.

Language: Английский

Citations

2
Computational Insights into the Reactivity Difference between Hypervalent Bromine(III) and Hypervalent Iodine(III) Reagent in the C−H Amination and Alkene Aziridination DOI

Yingbo Shao,

Zhiyuan Ren,

Chenfengtao Zheng

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(16), P. 2737 - 2743

Published: June 9, 2023

Abstract We present herein a computational exploration into the mechanism and origin of reactivity difference between N ‐triflylimino‐λ 3 ‐iodane ‐bromane in C−H amination alkene aziridination. Our calculations revealed that preferred for involves generation free nitrene intermediate, while aziridination proceeds via concerted reaction mechanism. The superior over could be mainly ascribed to better nucleofugality bromanyl moiety, which can characterized by strength I−N Br−N bond. effect solvent polarity on as precursor will discussed.

Language: Английский

Citations

2
Predicting bond dissociation energies of cyclic hypervalent halogen reagents using DFT calculations and graph attention network model DOI Creative Commons

Yingbo Shao,

Zhiyuan Ren,

Zhihui Han

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 1444 - 1452

Published: June 28, 2024

Although hypervalent iodine(III) reagents have become staples in organic chemistry, the exploration of their isoelectronic counterparts, namely bromine(III) and chlorine(III) reagents, has been relatively limited, partly due to challenges synthesizing stabilizing these compounds. In this study, we conduct a thorough examination both homolytic heterolytic bond dissociation energies (BDEs) critical for assessing chemical stability functional group transfer capability cyclic halogen compounds using density theory (DFT) analysis. A moderate linear correlation was observed between BDEs across different centers, while strong noted among centers. Furthermore, developed predictive model machine learning algorithms. The results study could aid estimating capabilities thereby facilitating development.

Language: Английский

Citations

0